Method for analyzing an impurity on a semiconductor substrate

Abstract: A method is provided for analyzing an impurity on a semiconductor substrate (12). In this method, those to-be-measured areas on a surface of a semiconductor substrate are exposed with an ultraviolet radiation (22) to provide corresponding oxide films (24). By doing so, an impurity is trapped in the oxide film at each area of the semiconductor substrate. The surface of the semiconductor substrate is cleaned with an acid solution to remove an impurity on other than the areas on the surface of the semiconductor substrate. The surface of the semiconductor substrate is exposed with a hydrofluoric acid vapor (28) to dissolve the oxide films (24) into very fine droplets (30) containing an impurity (26a). These droplets are moved on the surface of the semiconductor substrate to collect these droplets into a drop (32) on the surface of the semiconductor substrate. The impurity in the drop is measured by a known chemical spectrometer.

Description: The present invention relates to a method for analyzing an impurity present on the surface of a semiconductor substrate and, in particular, to a method for measuring an amount of impurity on a semiconductor substrate surface at a plurality of local areas. It has been known that a metal impurity is present on the surface of a semiconductor substrate or a semiconductor wafer and that the metal impurity, even if being very small in amounts, adversely affects the electric characteristics of a device. With a recent tendency toward realizing a high-density device, more and more exacting demand is made for the analysis of an impurity. There is also a high demand for the high-accurate analytical technique. In the conventional analytical method, a solution for impurity collection, such as an acid solution, is dropped on a whole surface area of a semiconductor substrate or on a nearly liquid-drop-size area on the surface of a semiconductor substrate where an impurity is collected. Then an amount of impurity collected in that solution used is measured by a chemical analytic apparatus such as a flameless atomic absorption apparatus. It has been known by an accelerated test that, on a semiconductor substrate having a surface pattern similar to a device surface pattern, the surface distribution pattern of an impurity concentration depends upon the surface pattern of the semiconductor substrate. The device surface pattern has become very small with the microminiaturization of the semiconductor element so that the surface distribution pattern of the impurity concentration becomes very small. Recently, the surface pattern of the device is of the order of a micrometer or submicrometer. On the other hand, the surface resolution by the conventional analytical method is of the order of a few cm 2 , an ordinary size of to-be-collected liquid drops at best, thus failing to achieve high-accurate analysis. DE-A-3 516 973 discloses a method for analyzing an impurity on a semiconductor substrate, characterised by comprising the steps of oxidizing a single to-be-measured area on a surface of a vertically arranged semiconductor substrate 23 by heating the surface using a laser or UV radiation to provide corresponding oxide films 26, 26 and trapping an impurity in the oxide film at the aforesaid area of the semiconductor substrate, dissolving the oxide films on the to-be-measured areas into droplets using hydrofluoric acid vapour which run downwardly, by gravity, along the vertical surface of the substrate and are received. in tray 25, and measuring the amount of impurity in the drop using a flameless atomic absorption spectrometer. It is an aim of the present invention to provide a method capable of accurately analyzing an amount of impurity on the surface of a semiconductor substrate. According to a first aspect of the present invention there is provided a method for analyzing an impurity on a semiconductor substrate, comprising the steps of: oxidizing a plurality of local to-be-measured areas on a surface of a semiconductor substrate and trapping impurities in the oxide film at each said area of the semiconductor substrate; removing the impurities from those areas on the surface of the semiconductor substrate where no oxide film is present; dissolving the oxide films on the to-be-measured areas into droplets formed on the to-be-measured areas; collecting the droplets into a drop by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop; and measuring the amount of impurities in the drop. According to a second aspect of the invention, there is provided a method for analyzing an impurity on a semiconductor substrate, characterized by comprising the steps of: depositing a nitride film on the whole surface of a semiconductor substrate and trapping impurities in the nitride film; forming a mask of a given pattern on the nitride film and selectively etching the nitride film using the mask to leave the nitride film at a plurality of to-be-measured areas on the substrate surface; dissolving the nitride film on the to-be-measured areas into droplets formed on the to-be-measured areas; collecting the droplets into a drop by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop; and measuring the amount of impurities in the drop. In a preferred way of putting the second aspect of the invention into effect the method further comprises the steps of repeating said nitride film depositing step to said measuring step, and plotting the amount of impurity obtained at each measuring step in a depth direction of said semiconductor substrate. According to a third aspect of the invention, there is provided a method for analyzing an impurity on a semiconductor substrate, characterized by comprising the steps of: oxidising the whole surface of a semiconductor substrate to form an oxide film and trapping impurities in the oxide film; forming a mask of a given pattern on the oxide film and selectively etching the oxide film using the mask to leave the oxide film at a plurality of to-be-measured areas on the substrate surface; dissolving the oxide film on the to-be-measured areas into droplets formed on the to-be-measured areas; collecting the droplets into a drop by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop; and measuring the amount of impurities in the drop. In a preferred way of putting either the first or third aspect of the invention into effect, the method further comprises the steps of repeating said oxidizing step to said measuring step, and plotting the amount of impurity obtained at each measuring step in a depth direction of said semiconductor substrate. This invention can be more fully understood from the following details description given by way of example, when taken in conjunction with the accompanying drawings, in which: FIG. 1 is a cross-sectional view showing a model showing a semiconductor substrate surface pattern; FIG. 2 is a cross-sectional view, taken along line II-II in FIG. 1; FIGS. 3A to 3D show the steps of a method for analyzing an amount of impurity on the surface of a semiconductor substrate in accordance with one example of the present invention, a view mainly showing a layer variation on the substrate surface; FIGS. 4A to 4D show initial steps of a method for analyzing an amount of impurity on the surface of a semiconductor substrate in accordance with another example of the present invention; and FIGS. 5A to 5D show initial steps of a method for analyzing an amount of impurity on the surface of a semiconductor substrate in accordance with another example of the present invention. FIG. 1 shows a model of a surface pattern on a semiconductor silicon substrate. A surface pattern layer 14 is formed of, for example, an insulating layer for semiconductor element isolation, providing a repeated pattern. Semiconductor element areas 16 are each formed by a semiconductor substrate surface area bounded by the isolation layer 14. In this embodiment, a respective local area 18 to be measured constitutes a portion of each element area, that is, those local areas 18 constitute mutually corresponding areas on the repeated pattern. FIG. 2 is a cross-sectional view, taken along line II-II in FIG. 1. In FIGS. 3A to 3D, the insulating pattern 14 for isolation is omitted for brevity's sake. The analytical examination is made by the following way. As shown in FIG. 3A, an ultraviolet radiation 22-is directed with a given pattern as a mask to those to-be-measured local areas 18 on the surface of a semiconductor silicon substrate 12 in a clean oxygen atmosphere. In FIG. 3A, an insulating layer pattern 14 for isolation is omitted for the sake of simplification. Then only the local area 18 irradiated with the ultraviolet radiation is oxidized by a heating process to form an oxide film 24, as a few nm-thick SiO 2 film, only on the areas to be measured. By doing so, an impurity 26a in the area on the substrate surface is trapped in the oxide film 24. The surface of the semiconductor substrate 12 is cleaned with a suitable detergent, such as an acid solution consisting of, for example, a hydrochloric acid/hydrogen peroxide-mixed aqueous solution. As shown in Fig. 3B, an impurity 26b on other than the to-be-treated area on the surface of the semiconductor substrate is removed. Thereafter, the resultant semiconductor substrate surface 12 is exposed with, for example, a hydrofluoric acid vapor to dissolve the oxide film 24, so that, as shown in FIG. 3C, very fine droplets (impurity drops) 30 containing the impurity are left on the surface of the substrate 12. About 100 to 500 µl of a liquid is dropped to the semiconductor substrate 12 and the very fine droplets (impurity collecting drops) are moved on the semiconductor substrate like in a scanning way to collect fine droplets 30 on the substrate surface and hence to provide a gathered drop 32 as shown in FIG. 3D. The liquid may be water, preferably, a high-purity acid solution consisting of, for example, a hydrochloric acid/hydrogen peroxide aqueous solution. Then an amount of impurity 26a in the gathered drop is measured by a known chemical spectrometer, such as a flameless atomic absorption spectrometer and inductively coupled plasma mass spectrometer. From the measured amount it is possible to calculate the concentration level of the impurity per unit area of the area to be measured. Any other measuring device may be used in place of the chemical spectrometer. As evident from the embodiment, it is possible according to the present invention to achieve a high surface resolution and hence to measure, with high accuracy, an amount of impurity 26a in the local areas 18 on the semiconductor substrate 12. In other words it it possible to highly accurately obtain the distribution characteristic from the amount of impurity on the surface of the semiconductor substrate 12. Although, in the above described method, the local areas on the substrate surface correspond to a regularly repeated pattern array on the semiconductor surface 12, the present method is not restricted thereto in that it is also possible to perform measurements in the -case of any plurality of local areas. The sensitivity of the present method under the chemical analysis, depending upon the size or area of the local area to be measured, is of the order of 10 9 to 10 10 atoms/cm 2 , a very high value than an ordinary sensitivity under a physical analysis of the order of 10 13 to 10 14 atoms/cm 2 . Even the impurity distribution characteristic of a pattern as small as a micrometer or sub-micrometer order under the pattern rule of a recent device can be obtained with high accuracy. In the above embodiment, the position of the surface portion of the semiconductor substrate 12 at which the oxide film 24 has been dissolved, is lowered in the depth direction of the semiconductor substrate 12. Therefore, after the step of collecting the very fine droplets 30, an insulating film is formed on those local areas, to be measured, on the resultant semiconductor substrate structure by the application of an ultraviolet radiation with the above-mentioned mask again used and, by doing so repetitively, a corresponding distribution characteristic is formed, each time, relative to the amount of impurity, so that amount-of-impurity distribution characteristics can be gained at different positions in a depth direction of the semiconductor structure, that is, it is possible to obtain amount-of-impurity distribution characteristics in the depth of the semiconductor structure by plotting these distribution characteristics in that depth direction. In the case where an impurity-free epitaxial layer is formed on a semiconductor wafer (semiconductor substrate), if those selected areas on the surface of the epitaxial layer are those spots to be measured, it is possible to, upon the formation of an oxide film, suppress the entry of an impurity from the semiconductor wafer into the oxide film. Therefore, those droplets collected contain only that impurity trapped in the epitaxial layer surface and more accurate analytic examination can be made for a metal impurity, such as Fe and Na, present on the surface of the semiconductor substrate. Although, in the above-mentioned embodiment, the oxide film 24 has been explained as being formed by an irradiation with the ultraviolet radiation and hence application of heat, it may be possible to utilize the exposure and hence heating of, for example, a laser beam. The formation of the oxide film 24 is not restricted only to the exposure of light. For example, an SiN film or SiO 2 film 42 is formed, by a known chemical vapor deposition method, on the whole surface of a semiconductor silicon substrate 12 as shown in FIG. 4A, or the whole surface is oxidised to form an oxide film, and a photoresist layer 44 whose pattern is an inverted version of a pattern for those to-be-measured areas on the semiconductor substrate is formed by a known method on the SiO 2 film 42 as shown in FIG. 4B. Then only those SiO 2 film 42 portions on these areas are left, by a selective etching, on the semiconductor substrate 12 with the photoresist layer 44 used as a mask as shown in FIG. 4C, followed by the elimination of the photoresist layer 44. By doing so it may be possible to obtain those SiN or SiO 2 film 42 portions as shown in FIG. 4D. The oxide film 42 may be replaced with a nitride film. Forming the nitride film can be achieved in substantially the same way as in the case where the SiO 2 film 42 is formed on the substrate as shown in FIGS. 4A to 4D. That is, an SiN film 52 is formed, by a known chemical vapor deposition method, on the whole surface of a semiconductor silicon substrate 12 as shown in FIG. 5A and a photoresist layer 54 whose pattern is an inverted version of a pattern for those to-be-measured areas on a semiconductor substrate 12 is formed, by a known method, on the SiN film 52 as shown in FIG. 5B. Then the surface of the resultant semiconductor structure is selectively etched with a photoresist layer 54 used as a mask to leave only those to-be-measured areas of the SiN film 52 on the surface of the semiconductor device as shown in FIG. 5C, followed by the elimination of the photoresist layer 54 as shown in FIG. 5D. The remaining processing steps are the same as those using the SiO 2 film set out in conjunction with FIGS. 3C and 3D. As evident from the above explanation, according to the present method, it is possible to realize a high surface resolution. It is possible to highly accurately measure an amount of impurity on local areas on the semiconductor substrate 12 and hence to highly accurately obtain a distribution characteristic relating to an amount of impurity on the surface of a semiconductor substrate 12.

Claims: A method for analyzing an impurity on a semiconductor substrate, comprising the steps of: oxidizing a plurality of local to-be-measured areas on a surface of a semiconductor substrate (12) and trapping impurities (26a) in the oxide film (24) at each said area of the semiconductor substrate; removing the impurities (26b) from those areas on the surface of the semiconductor substrate where no oxide film is present; dissolving the oxide films on the to-be-measured areas into droplets (30) formed on the to-be-measured areas; collecting the droplets (30) into a drop (32) by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop (32); and measuring the amount of impurities (26a) in the drop (32). A method for analyzing an impurity on a semiconductor substrate, characterized by comprising the steps of: depositing a nitride film (52) on the whole surface of a semiconductor substrate (12) and trapping impurities (26a) in the nitride film; forming a mask (54) of a given pattern on the nitride film and selectively etching the nitride film using the mask to leave the nitride film at a plurality of to-be-measured areas on the substrate surface; dissolving the nitride film (52) on the to-be-measured areas into droplets (30) formed on the to-be-measured areas; collecting the droplets (30) into a drop (32) by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop (32); and measuring the amount of impurities in the drop (32). A method for analyzing an impurity on a semiconductor substrate, characterized by comprising the steps of: oxidising the whole surface of a semiconductor substrate (12) to form an oxide film (42) and trapping impurities (26a) in the oxide film; forming a mask (44) of a given pattern on the oxide film and selectively etching the oxide film using the mask to leave the oxide film at a plurality of to-be-measured areas on the substrate surface; dissolving the oxide film (42) on the to-be-measured areas into droplets (30) formed on the to-be-measured areas; collecting the droplets (30) into a drop (32) by dropping a liquid onto the surface of the semiconductor substrate and moving the liquid on the substrate surface to form the drop (32); and measuring the amount of impurities in the drop (32). A method according to claim 1 or 3, further comprising the steps of: repeating said oxidizing step to said measuring step; and plotting the amount of impurity (26a) obtained at each measuring step in a depth direction of said semiconductor substrate. The method according to claim 1 or 4, characterised in that the oxide film (24) is formed on the to-be-measured areas by emitting an ultraviolet radiation on these areas to apply heat there. The method according to claim 1 or 4, characterised in that the oxide film (24) is formed on the to-be-measured areas by emitting a laser beam on these areas to apply heat there. The method according to claim 1 or 4, characterised in that the oxide film (24) is dissolved by exposing the surface of the semiconductor substrate to a hydrofluoric acid vapour. The method according to claim 1 or 4, characterised in that the collection of the droplets is effected by moving an acid solution on the surface of the semiconductor substrate in a scanning way. A method according to claim 2, further comprising the steps of: repeating said nitride film depositing step to said measuring step; and plotting the amount of impurity (26a) obtained at each measuring step in a depth direction of said semiconductor substrate. The method according to claim 1 or 4, characterised in that the removal of the impurity (26b) is effected by washing the surface of the semiconductor substrate with an acid solution. The method according to claim 8 or 10, characterised in that the acid solution consists of a hydrochloric acid/hydrogen peroxide-mixed aqueous solution. The method according to claim 2, characterised in that the nitride film is dissolved by exposing the surface of the semiconductor substrate to a hydrofluoric acid vapour. The method according to any one of claims 1 to 4, characterised in that the collection of the droplets (30) are effected by moving these droplets in a scanning way. The method according to any one of claims 1 to 4, characterised in that the amount of impurity (26a) is measured by a chemical analysis. The method according to claim 14, characterised in that the chemical analysis is made by a flameless atomic absorption spectrometer. The method according to claim 14, characterised in that the chemical analysis is made by an inductive coupled plasma mass spectrometer.

Inventors: SHIMAZAKI AYAKO, SHIMAZAKI, AYAKO, SHIMAZAKI, AYAKO, C/O INTELL. PROPERTY DIV.
Applicants: TOSHIBA KK, KABUSHIKI KAISHA TOSHIBA
Application year: 1994
Main classification: H01L21
IPC codes: G01N1, H01L21